Agricultural residues represent a disposal problem and a biomass source for chemical production. Lignocellulosic composition varies in plants as a function of several factors such as physiological age and tissue function. Banana pseudostem is a large biomass resource that is usually wasted, in spite of the possibility that it can be used as a source of organic compounds such as cellulose and hemicelluloses. The aim of this paper is compare the lignocellulosic content and physicochemical properties of different sheaths of Pacovan banana pseudostems. The trunk was divided into four different fractions, from the outermost sheaths to the core of the structure. There was a significant difference between the lignocellulosic compositions of the fractions. The X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry measurements reflected this difference in the sheaths. These results indicate that the Pacovan banana pseudostem cannot be considered to be a uniform biomass, and future approaches to its use as a biorefinery feedstock must consider a preliminary separation of the sheaths prior to chemical extraction of organic components.